JP5069487B2 - Heat sensitive adhesive material - Google Patents

Description

  The present invention has a heat-sensitive pressure-sensitive adhesive layer that is non-adhesive at normal temperature but develops adhesiveness upon heating, and that persists even after the occurrence of adhesiveness, particularly for rough surface adherends such as cardboard The present invention relates to a heat-sensitive adhesive material excellent in adhesive strength under a wide temperature environment from low temperature (0 ° C.) to high temperature (40 ° C.).

In recent years, adhesive label sheets have been increasingly used for purposes such as price display labels, product display (barcode) labels, quality display labels, weighing display labels, and advertising labels (stickers). As for the label recording method, various methods such as an ink jet recording method, a thermal recording method, and a pressure sensitive recording method have been developed.
Such an adhesive label sheet generally has a structure in which an adhesive layer and release paper are laminated on the surface opposite to the information recording surface of the label. Widely used because it can be pasted together. In general, the pressure-sensitive adhesive label sheet is used after the release paper is peeled off. However, the peeled release paper is difficult to collect and reuse and is discarded in most cases. Therefore, recently, a heat-sensitive adhesive label sheet using a heat-sensitive adhesive material having a heat-sensitive adhesive layer that does not exhibit adhesiveness at room temperature, develops adhesiveness by heating, and does not require a release paper has attracted attention. (See Patent Document 1).

The heat-sensitive pressure-sensitive adhesive layer in such a heat-sensitive pressure-sensitive adhesive label sheet contains at least a thermoplastic resin and a hot-melt material, and further contains a tackifier as necessary (see Non-Patent Document 1). However, the heat-sensitive pressure-sensitive adhesive layer in the heat-sensitive pressure-sensitive adhesive label sheet decreases in adhesive strength over time after developing the pressure-sensitive adhesive property. Moreover, it is necessary to give a high thermal energy at the time of thermal activation.
In order to improve this point, for example, by providing a heat insulating layer containing plastic hollow particles and a water-soluble binder between the support and the heat-sensitive adhesive layer, the thermal energy is reduced during thermal activation. (In other words, high sensitivity) has been proposed (see Patent Documents 2 to 3).
However, these proposed heat-sensitive adhesive label sheets are effective in reducing thermal energy when the heat-sensitive adhesive layer is thermally activated, but a water-soluble binder that does not exhibit adhesiveness at room temperature. Since it is used, the adhesive strength to rough adherends such as cardboard has not reached the practical level.
Furthermore, the problem that the adhesive strength after expressing the adhesiveness decreases with time has not been solved.

Recently, the present inventors have proposed a thermosensitive adhesive label sheet having an adhesive under layer containing a thermoplastic resin having a glass transition temperature (Tg) of −70 to 0 ° C. and a filler in Patent Document 4. . This thermosensitive pressure-sensitive adhesive label sheet can obtain a good adhesive force to rough surface adherends such as corrugated cardboard even by thermal head heating in a normal temperature and normal humidity environment (23 ° C., 65%). However, this thermosensitive pressure-sensitive adhesive label sheet has insufficient adhesion to rough surfaces such as corrugated cardboard in a low-temperature environment of 0 to 10 ° C. In order to increase the adhesion in a low-temperature environment, When the resin is increased, there is a problem that the blocking quality is lowered.
Patent Documents 5 to 13 propose a heat-sensitive adhesive material containing a phosphorus compound such as triphenylphosphine as a hot-melt material (sometimes referred to as “solid plasticizer”) in the heat-sensitive adhesive layer. Yes. However, in these proposals, a large amount of thermal energy is required for thermal activation, and sufficient adhesive strength cannot be obtained by thermal activation with a thermal head. Furthermore, the effect of improving blocking resistance is insufficient, and there are many problems in practical use at present.

In order to solve the above problem, the inventors of the prior application (Japanese Patent Application No. 2006-207472) provided a support and at least an under layer and a heat-sensitive adhesive layer on one surface of the support in this order. And the under layer contains a thermoplastic resin having a glass transition temperature (Tg) of −35 to 25 ° C. and a hollow filler, and the thermoplastic resin is selected from a styrene-butadiene copolymer and a modified product thereof The heat-sensitive adhesive layer contains a thermoplastic resin, a tackifier, and a hot melt substance, and the hot melt substance contains at least triphenylphosphine. A heat-sensitive adhesive material is proposed.
This heat-sensitive adhesive material has a strong adhesive force to rough surface adherends such as corrugated cardboard at a low temperature (0 ° C.) to room temperature (23 ° C.), and there is little decrease in the adhesive force over time. There is a problem that the adhesive strength within 2 minutes immediately after being applied in the temperature range is slightly weak.

Japanese Utility Model Publication No. 6-25869 Japanese Patent No. 2683733 Japanese Patent Laid-Open No. 10-152660 JP 2006-111865 A JP 2000-103969 A JP 2000-191920 A JP 2000-191922 A JP 2000-21527 A JP 2001-64401 A JP 2001-262117 A JP 2002-88678 A JP 2002-338935 A Japanese Patent Laid-Open No. 2004-117941 "Adhesion Handbook" 12th edition, pp. 131-135, published in 1970

  The present invention has a strong adhesive force in a wide temperature range from a low temperature (0 ° C.) to a high temperature (40 ° C.), particularly on a rough surface adherend such as corrugated cardboard. It is an object of the present invention to provide a heat-sensitive adhesive material that can be thermally activated with low energy by a thermal head and has good blocking resistance.

（式中、Ｒ^１、Ｒ^２は、互いに同一でも異なっていてもよく、水素原子、炭素数が1〜８のアルキル基、α，α−ジメチルベンジル基の何れかを表し、Ｒ^３は、水素原子又は塩素原子を表す。）
＜２＞ 熱溶融物質中のトリフェニルホスフィンの含有量が８０〜９０重量％である＜１＞記載の感熱性粘着材料
＜３＞ 中空フィラーが、体積平均粒子径２．０〜５．０μｍの球状中空粒子であり、かつ該球状中空粒子の中空率が７０％以上である＜１＞又は＜２＞記載の感熱性粘着材料。
＜４＞ 球状中空粒子の材料が、塩化ビニリデン−アクリロニトリル共重合体、アクリロニトリル−塩化ビニリデン−メタクリル酸メチル共重合体、及びアクリロニトリル−メタクリロニトリル−イソボニルメタクリレート共重合体の何れかである＜３＞記載の感熱性粘着材料。
＜５＞ アンダー層における熱可塑性樹脂と中空フィラーの混合割合が、熱可塑性樹脂１重量部に対し中空フィラー０．１〜２重量部である＜１＞〜＜４＞の何れかに記載の感熱性粘着材料。
＜６＞ アンダー層に隣接する感熱性粘着剤層の乾燥付着量が１０〜２０ｇ／ｍ^２である＜１＞〜＜５＞の何れかに記載の感熱性粘着材料。
＜７＞ 支持体の感熱性粘着剤層を有しない側の面上に少なくとも感熱記録層を有し、かつ該感熱記録層が少なくともロイコ染料及び顕色剤を含有する＜１＞〜＜６＞の何れかに記載の感熱性粘着材料。
＜８＞ その形状が、ラベル状、シート状、ラベルシート状、及びロール状の何れかである＜１＞〜＜７＞の何れかに記載の感熱性粘着材料。 The above problems are solved by the following inventions <1> to < 8 >.
<1> On one surface of the support, at least an under layer and a heat-sensitive adhesive layer are provided in this order, and the under layer has a glass transition temperature (Tg) of −35 to 25 ° C. thermoplastic resin and hollow. A filler, and the thermoplastic resin contains a styrene-butadiene copolymer or a carboxy-modified styrene-butadiene copolymer, and the heat-sensitive adhesive layer comprises a thermoplastic resin, a tackifier, a hot-melt material, and A heat-sensitive adhesive material comprising silicone resin particles, wherein the hot-melt material is triphenylphosphine and a benzotriazole compound represented by the following general formula (1).

(Wherein, R ^1, R ^2, which may be the same or different from each other, represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, alpha, any of α- dimethylbenzyl, R ³ is Represents a hydrogen atom or a chlorine atom.)
<2> The heat-sensitive adhesive material according to <1>, wherein the content of triphenylphosphine in the hot-melt material is 80 to 90% by weight. < 3 > The hollow filler has a volume average particle size of 2.0 to 5.0 μm. The heat-sensitive adhesive material according to <1> or <2> , which is a spherical hollow particle, and the hollow ratio of the spherical hollow particle is 70% or more.
< 4 > The material of the spherical hollow particles is any one of vinylidene chloride-acrylonitrile copolymer, acrylonitrile-vinylidene chloride-methyl methacrylate copolymer, and acrylonitrile-methacrylonitrile-isobornyl methacrylate copolymer <3 > The heat-sensitive adhesive material described.
< 5 > The thermal sensitivity according to any one of <1> to <4>, wherein the mixing ratio of the thermoplastic resin and the hollow filler in the under layer is 0.1 to 2 parts by weight of the hollow filler with respect to 1 part by weight of the thermoplastic resin. Adhesive material.
< 6 > The heat-sensitive adhesive material according to any one of <1> to < 5 >, wherein the dry adhesion amount of the heat-sensitive adhesive layer adjacent to the under layer is 10 to ²⁰ g / m ² .
< 7 ><1> to < 6 > having at least a heat-sensitive recording layer on the surface of the support that does not have the heat-sensitive adhesive layer, and the heat-sensitive recording layer containing at least a leuco dye and a developer. The heat-sensitive adhesive material according to any one of the above.
< 8 > The heat-sensitive adhesive material according to any one of <1> to < 7 >, wherein the shape is any one of a label shape, a sheet shape, a label sheet shape, and a roll shape.

Hereinafter, the present invention will be described in detail.
The heat-sensitive adhesive material of the present invention has a support and at least an under layer and a heat-sensitive adhesive layer in this order on one side of the support, and the under layer has a glass transition temperature (Tg) of − A thermoplastic resin having a temperature of 35 to 25 ° C. and a hollow filler, and the thermoplastic resin contains a styrene-butadiene copolymer or a carboxy-modified styrene-butadiene copolymer. A plastic resin, a tackifier, a hot melt substance, and silicone resin particles are contained, and the hot melt substance contains triphenylphosphine and a benzotriazole compound represented by the general formula (1).
As a result, the adhesive strength against a rough surface adherend such as corrugated cardboard is strong under a wide temperature environment from low temperature (0 ° C.) to high temperature (40 ° C.), and there is little decrease in the adhesive strength with time. Thus, a heat-sensitive adhesive material can be obtained, which can be activated by heat and has good blocking resistance.
The heat-sensitive adhesive material of the present invention may have other layers as needed in addition to the support, the under layer and the heat-sensitive adhesive layer. In addition, it is preferable to have at least a heat-sensitive recording layer on the other surface that does not have the under layer and the heat-sensitive adhesive layer of the support.

Next, each element which comprises the said thermosensitive adhesive material is demonstrated in order.
<Support>
The shape, structure, size and the like of the support are not particularly limited and can be appropriately selected according to the purpose. Examples of the shape include a flat plate shape, and the structure is a single layer structure. Alternatively, a laminated structure may be used, and the size can be appropriately selected according to the size of the heat-sensitive adhesive material.
The material for the support is not particularly limited and may be appropriately selected depending on the intended purpose. Examples of the inorganic material include glass, quartz, silicon, silicon oxide, aluminum oxide, SiO ₂ and metal. . Examples of organic materials include paper such as fine paper, art paper, coated paper, and synthetic paper; cellulose derivatives such as cellulose triacetate; polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate; polycarbonate, polystyrene, and polymethyl Examples thereof include polyolefins such as methacrylate, polyamide, polyethylene, and polypropylene. Among these, fine paper, coated paper, plastic film, and synthetic paper are particularly preferable.
The support is preferably subjected to surface modification such as corona discharge treatment, oxidation reaction treatment (chromic acid, etc.), etching treatment, easy adhesion treatment, antistatic treatment, etc. for the purpose of improving the adhesion of the coating layer. Further, it is preferable to add a white pigment such as titanium oxide to the support.
There is no restriction | limiting in particular in the thickness of a support body, Although it can select suitably according to the objective, 50-2,000 micrometers is preferable and 100-1,000 micrometers is more preferable.

<Under layer>
The under layer contains at least a thermoplastic resin and a hollow filler, and further contains other components as necessary.
-Thermoplastic resin-
The glass transition temperature (Tg) of the thermoplastic resin is −35 to 25 ° C., preferably −35 to 5 ° C. When Tg exceeds 25 ° C., the binding force and interlayer binding force of the hollow filler may be weakened, and the adhesive strength to the adherend may be weakened. If it is lower than −35 ° C., blocking resistance may be lowered.
As the thermoplastic resin, a styrene-butadiene copolymer or a carboxy-modified styrene-butadiene copolymer having a Tg of −35 to 25 ° C. is used.

-Hollow filler-
As the hollow filler, spherical plastic hollow particles having a volume average particle diameter of 2.0 to 5.0 μm and a hollow ratio of 70% or more are preferable, and the maximum particle diameter of the hollow particles is 10.0 μm or less, Spherical hollow particles having an average particle diameter of 2.0 to 5.0 μm and a hollow ratio of 70% or more are more preferable. The hollowness is more preferably 85 to 95%.
If the hollow ratio is less than 70%, the heat insulation effect is insufficient, so that heat energy from the thermal head is released to the outside through the support, and a highly sensitive heat activation effect may not be obtained. In addition, when the volume average particle diameter exceeds 5.0 μm, when the heat-sensitive adhesive layer is provided on the under layer using such a hollow filler, the heat-sensitive adhesive layer is not formed due to large particles. When it is thermally activated, the adhesive strength tends to decrease. If it is less than 2.0 μm, it becomes difficult to ensure a hollow ratio of 70% or more, and a highly sensitive thermal activation effect is obtained. It may not be possible.
The plastic spherical hollow particle means a hollow particle which is already foamed with a thermoplastic resin as a shell and containing air or other gas inside. Moreover, the hollow ratio here is the ratio of the volume of the internal void portion to the entire volume of the hollow particles.
The material for the spherical hollow particles is not particularly limited and may be appropriately selected depending on the purpose. For example, vinylidene chloride-acrylonitrile copolymer, acrylonitrile-vinylidene chloride-methyl methacrylate copolymer, acrylonitrile-methacrylo Nitrile-isobornyl methacrylate copolymer and the like are preferable.

The mixing ratio of the thermoplastic resin having a Tg of −35 to 25 ° C. and the hollow filler in the under layer is preferably 0.1 to 2 parts by weight of the hollow filler, and 0.3 to 1 part by weight with respect to 1 part by weight of the thermoplastic resin. Is more preferable. If the hollow filler is less than 0.1 part by weight, a highly sensitive thermal activation effect may not be obtained, and if it exceeds 2 parts by weight, the binding force of the under layer may be inferior and the adhesive strength may be weakened.
The under layer can be formed according to a known method. For example, the under layer is formed by a coating method using an under layer coating liquid containing the above components.
Examples of coating methods include blade coating, gravure coating, gravure offset coating, bar coating, roll coating, knife coating, air knife coating, comma coating, U comma coating, AKKU coating, Examples thereof include a smoothing coating method, a micro gravure coating method, a reverse roll coating method, a four or five roll coating method, a dip coating method, a falling curtain coating method, a slide coating method, and a die coating method.
The coating amount of the under layer coating solution is preferably 1 to 35 g / m ^{2 and} more preferably ² to 25 g / m ^{2 in} terms of dry coating amount. If the coating amount is less than 1 g / m ² , sufficient adhesion cannot be obtained when performing adhesion by heating, and the heat insulation effect may be inferior. If it exceeds 35 g / m ² , the adhesion and heat insulation effect are saturated. May end up.

<Thermosensitive adhesive layer>
The heat-sensitive adhesive layer contains at least a thermoplastic resin, a tackifier, a hot melt substance, and silicone resin particles, but may contain other components as necessary.
-Hot melt material-
Since the hot-melt material is solid at normal temperature, it does not give plasticity to the resin, but it melts by heating and swells or softens the resin, expresses adhesiveness, melts by heating, and then slowly crystallizes. It is a substance that can maintain stickiness for a long time even after the heat source is removed.
The hot-melt material must necessarily contain triphenylphosphine and the benzotriazole compound represented by the general formula (1).
Triphenylphosphine is an organophosphorus compound represented by the following structural formula and may be abbreviated as TPP. It is relatively stable to air, is a crystalline solid at room temperature, and is soluble in nonpolar organic solvents such as benzene. The molecular weight is 262.3 and the melting point is 79-81 ° C.

Examples of the benzotriazole compound represented by the general formula (1) include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-5′-t-octylphenyl). ) Benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-) Amylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-t-butylphenyl) -5-chlorobenzotriazole, 2- [2'-hydroxy-3', 5'-di (1, 1-dimethylbenzyl) phenyl] benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy- '-S-butyl-5'-t-butylphenyl) benzotriazole.
These may be used individually by 1 type and may use 2 or more types together.

By making the volume average particle diameter of the above hot-melt material 0.5 μm or less, dynamic thermal sensitivity is increased, and it becomes compatible with a thermoplastic resin and a tackifier at low energy to become a thermoactive adhesive. This improves the storage stability at the temperature of the storage environment (improves blocking resistance).
The total content of triphenylphosphine and the benzotriazole compound represented by the general formula (1) in the heat-sensitive adhesive layer is preferably 25 to 80% by weight, and more preferably 35 to 70% by weight. When the total content is less than 25% by weight, when combined with a thermoplastic resin, storage problems such as adhesive strength appearing under normal storage environment temperature (blocking) may occur, or adhesive strength may decrease. In some cases, if it exceeds 80% by weight, the adhesive strength may be lowered.
The content of triphenylphosphine in the hot melt material is preferably 80 to 90% by weight. If the content of triphenylphosphine is less than 80% by weight, the adhesive force immediately after pasting at 23 to 40 ° C. may be weak, and if it exceeds 90% by weight, the delay property may be reduced and the adhesive force may be reduced. .

-Thermoplastic resin-
The thermoplastic resin is not particularly limited and may be appropriately selected depending on the purpose. However, when a resin similar to the thermoplastic resin used for the adhesive under layer is used, the compatibility of the resins in both layers is improved. Therefore, it is preferable because the adhesive force to a rough surface adherend such as cardboard is improved.
Examples of the thermoplastic resin include natural rubber latex obtained by graft copolymerization with a vinyl monomer, acrylic ester copolymer, methacrylic ester copolymer, acrylic ester-methacrylic ester copolymer, acrylic ester-styrene. A copolymer, an acrylic ester-methacrylic ester-styrene copolymer, an ethylene-vinyl acetate copolymer, etc. are mentioned.
These may be used individually by 1 type and may use 2 or more types together.
The content of the thermoplastic resin in the heat-sensitive adhesive layer is preferably 10 to 60% by weight, and more preferably 15 to 50% by weight. When the content is less than 10% by weight or more than 60% by weight, both of them are not preferable because the adhesive strength is lowered. On the other hand, if the content of the resin having a low Tg exceeds 60% by weight, there may be a storage defect (blocking) such as an adhesive force developed at a normal storage environment temperature.

-Tackifier-
The tackifier is added to improve the adhesive strength of the heat-sensitive adhesive layer, and is not particularly limited and can be appropriately selected from known ones according to the purpose. For example, a rosin derivative (rosin , Polymerized rosin, hydrogenated rosin, etc.), terpene resins (terpene resins, aromatic modified terpene resins, terpene phenol resins, hydrogenated terpene resins, etc.), petroleum resins, phenol resins, xylene resins and the like. These tackifiers are compatible with the thermoplastic resin and the hot melt material, and can significantly improve the adhesive strength of the heat-sensitive adhesive layer.
The melting point (or softening point) of the tackifier is preferably 80 ° C. or higher, and more preferably 80 to 200 ° C. If the melting point (or softening point) is less than 80 ° C., storage defects (decrease in blocking resistance) may occur at normal storage environment temperatures.
1-30 weight% is preferable and, as for content of the tackifier in a heat-sensitive adhesive layer, 1-20 weight% is more preferable. If the content is less than 1% by weight, the adhesive strength may be remarkably reduced. If the content exceeds 30% by weight, storage troubles (decrease in blocking resistance) at normal storage environment temperatures and low temperature environments may occur. Decrease in initial adhesive strength may occur.

When silicone resin particles are contained in the heat-sensitive adhesive layer, the blocking resistance is improved.
As the silicone resin particles, for example, organic fillers such as silicone rubber, silicone resin particles, and composite particles of silicone rubber and silicone resin are preferable. It is considered that these resin particles not only have excellent releasability in blocking resistance, but also have a spherical structure that enhances the effect. Further, when considering the stickiness expression (activation) by the thermal head, the thermal head has the characteristic that the damage to the thermal head is small and the head matching property is excellent.
The content of the silicone resin particles in the heat-sensitive adhesive layer is preferably 0.5 to 2.0 parts by weight and more preferably 0.7 to 1.2 parts by weight with respect to 1 part by weight of the thermoplastic resin. If the amount is less than 0.5 part by weight, the effect of improving the blocking resistance may not be sufficiently exhibited. If the amount exceeds 2.0 parts by weight, the tackiness may be lowered.
If necessary, other components such as a eutectic agent, a dispersant, an antifoaming agent and a thickener can be added to the heat-sensitive adhesive layer.

There is no restriction | limiting in particular in the formation method of an adhesion under layer, It can form by well-known methods, such as a coating method and a printing method.
Examples of coating methods include blade coating, gravure coating, gravure offset coating, bar coating, roll coating, knife coating, air knife coating, comma coating, U comma coating, AKKU coating, and smoothing. Examples thereof include a coating method, a micro gravure coating method, a reverse roll coating method, a four or five roll coating method, a dip coating method, a falling curtain coating method, a slide coating method, and a die coating method.
In addition, as drying conditions at the time of application | coating or printing, you have to set it as the temperature range which the hot-melt substance to be used does not melt | dissolve. As a means for drying, in addition to hot air drying, a drying method using a heat source using infrared rays, microwaves, and high frequencies can be used.

The dry coating amount of the heat-sensitive adhesive layer coating solution (dry adhesion amount of the heat-sensitive adhesive layer) is preferably 10 to ²⁰ g / m ² . When the coating amount is less than 10 g / m ² , sufficient adhesive strength may not be obtained when pasting at a low temperature. When the coating amount exceeds 20 g / m ² , the heat insulating effect of the under layer is diminished or the economy is inferior. This is not preferable.
The heat-sensitive adhesive material of the present invention has the above-described structure, and thus has a strong adhesive force even in a low temperature environment of 0 ° C. to 10 ° C. and low adhesion to various adherends, particularly rough adherends such as cardboard. It can be activated by energy and has good blocking resistance.

Next, the heat-sensitive adhesive material of the present invention preferably has at least a heat-sensitive recording layer on the side of the support that does not have the heat-sensitive adhesive layer, and includes a protective layer, an intermediate layer, and other if necessary It has a layer of.
The heat-sensitive recording layer contains at least a leuco dye, a developer, and a binder resin, and further contains other components such as a filler as necessary.
The leuco dye is not particularly limited and can be appropriately selected from known ones according to the purpose. For example, triphenylmethane dyes, fluoran dyes, phenothiazine dyes, auramine dyes, spiropyran dyes, Indoline phthalide dyes are listed.

  Specific examples of the leuco dye include 3,3-bis (p-dimethylaminophenyl) phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (also called crystal violet lactone), 3, 3-bis (p-dimethylaminophenyl) -6-diethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) -6-chlorophthalide, 3,3-bis (p-dibutylaminophenyl) phthalide, 3- Cyclohexylamino-6-chlorofluorane, 3-dimethylamino-5,7-dimethylfluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-7-methylfluorane, 3-diethylamino-7,8- Benzfluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3- (N p-tolyl-N-ethylamino) -6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 2- {N- (3'-trifluoromethylphenyl) Amino} -6-diethylaminofluorane, 3-diethylamino-6-methyl-7- (m-trichloromethylanilino) fluorane, 3-diethylamino-7- (o-chloroanilino) fluorane, 3-dibutylamino-7- ( o-chloroanilino) fluorane, 3-N-methyl-N-amylamino-6-methyl-7-anilinofluorane, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluorane, 3 -Diethylamino-6-methyl-7-anilinofluorane, 3- (N, N-diethylamino) -5-methyl-7- (N, N- Benzylamino) fluorane, benzoylleucomethylene blue, 6'-chloro-8'-methoxy-benzoindolino-pyrospirane, 6'-bromo-3'-methoxy-benzoindolino-pyrospirane, 3- (2'-hydroxy-4 '-Dimethylaminophenyl) -3- (2'-methoxy-5'-chlorophenyl) phthalide, 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2'-methoxy-5'- Nitrophenyl) phthalide, 3- (2'-hydroxy-4'-diethylaminophenyl) -3- (2'-methoxy-5'-methylphenyl) phthalide, 3-diethylamino-6-methyl-7- (2 ', 4'-dimethylanilino) fluorane, 3- (2'-methoxy-4'-dimethylaminophenyl) -3- (2'-hy Droxy-4'-chloro-5'-methylphenyl) phthalide, 3-morpholino-7- (N-propyl-trifluoromethylanilino) fluorane, 3-pyrrolidino-7-trifluoromethylanilinofluorane, 3- Diethylamino-5-chloro-7- (N-benzyl-trifluoromethylanilino) fluorane, 3-pyrrolidino-7- (di-p-chlorophenyl) methylaminofluorane, 3-diethylamino-5-chloro-7- (Α-phenylethylamino) fluorane, 3- (N-ethyl-p-toluidino) -7- (α-phenylethylamino) fluorane, 3-diethylamino-7- (o-methoxycarbonylphenylamino) fluorane, 3- Diethylamino-5-methyl-7- (α-phenylethylamino) fluorane, 3-die Ruamino-7-piperidinofluorane, 2-chloro-3- (N-methyltoluidino) -7- (pn-butylanilino) fluorane, 3- (N-benzyl-N-cyclohexylamino) -5,6- Benzo-7-α-naphthylamino-4'-o-bromofluorane, 3-diethylamino-6-methyl-7-mesitidino-4 ', 5'-benzofluorane, 3-diethylamino-6-methyl-7- (2 ', 4'-dimethylanilino) fluorane, 3- (p-dimethylaminophenyl) -3- {1,1-bis (p-dimethylaminophenyl) ethylene-2-yl} phthalide, 3- (p -Dimethylaminophenyl) -3- {1,1-bis (p-dimethylaminophenyl) ethylene-2-yl} -6-dimethylaminophthalide, 3- (p-dimethylamino) Phenyl) -3- (1-p-dimethylaminophenyl-1-phenylethylene-2-yl) phthalide, 3- (p-dimethylaminophenyl-3- (1-p-dimethylaminophenyl-1-p-chlorophenyl) Ethylene-2-yl) -6-dimethylaminophthalide, 3- (4'-dimethylamino-2'-methoxy) -3- (1 "-p-dimethylaminophenyl-1" -p-chlorophenyl-1 " , 3 ″ -butadiene-4 ″ -yl) benzophthalide, 3- (4′-dimethylamino-2′-benzyloxy) -3- (1 ″ -p-dimethylaminophenyl-1 ″ -phenyl-1 ″, 3 "-Butadiene-4" -yl) benzophthalide, 3-dimethylamino-6-dimethylamino-fluorene-9-spiro-3 '-(6'-dimethylamino) phthalide, 3 3-bis {2- (p-dimethylaminophenyl) -2- (p-methoxyphenyl) ethenyl} -4,5,6,7-tetrachlorophthalide, 3-bis {1,1-bis (4- Pyrrolidinophenyl) ethylene-2-yl} -5,6-dichloro-4,7-dibromophthalide, bis (p-dimethylaminostyryl) -1-naphthalenesulfonylmethane, 3- (N-methyl-N-propyl) Amino) -6-methyl-7-anilidefluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3,6-bis (dimethylamino) fluorane spiro (9,3 ')-6'- Dimethylaminophthalide, 3-diethylamino-6-chloro-7-anilinofluorane, 3-N-ethyl-N- (2-ethoxypropyl) amino-6-methyl-7-anilinofur Lan, 3-N-ethyl-N-tetrahydrofurfurylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-mesitidino-4 ', 5'-benzofluorane, 3- N-methyl-N-isobutyl-6-methyl-7-anilinofluorane, 3-N-ethyl-N-isoamyl-6-methyl-7-anilinofluorane and the like can be mentioned. These may be used individually by 1 type and may use 2 or more types together.

The developer is not particularly limited and can be appropriately selected from known electron-accepting compounds according to the purpose. For example, phenolic compounds, thiophenolic compounds, thiourea derivatives, organic acids or The metal salt etc. are mentioned.
Specific examples of the developer include 4,4'-isopropylidenebisphenol, 3,4'-isopropylidenebisphenol, 4,4'-isopropylidenebis (o-methylphenol), 4,4'-s-butyl Ridenbisphenol, 4,4'-isopropylidenebis (ot-butylphenol), 4,4'-cyclohexylidenediphenol, 4,4'-isopropylidenebis (2-chlorophenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-butylidenebis (6-t-butyl-2-methyl) phenol, 1 , 1,3-Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,1,3-tris (2-methyl 4-hydroxy-5-cyclohexylphenyl) butane, 4,4'-thiobis (6-tert-butyl-2-methyl) phenol, 4,4'-diphenolsulfone, 4,2'-diphenolsulfone, 4- Isopropoxy-4'-hydroxydiphenylsulfone, 4-benzyloxy-4'-hydroxydiphenylsulfone, 4,4'-diphenol sulfoxide, isopropyl P-hydroxybenzoate, benzyl P-hydroxybenzoate, benzyl protocatechuate, gallic acid Stearyl, lauryl gallate, octyl gallate, 1,7-bis (4-hydroxyphenylthio) -3,5-dioxaheptane, 1,5-bis (4-hydroxyphenylthio) -3-oxaheptane, 1 , 3-bis (4-hydroxyphenylthio) -propane, 2, '-Methylenebis (4-ethyl-6-tert-butylphenol), 1,3-bis (4-hydroxyphenylthio) -2-hydroxypropane, N, N'-diphenylthiourea, N, N'-di (m -Chlorophenyl) thiourea, salicylanilide, 5-chloro-salicylanilide, salicyl-o-chloroanilide, 2-hydroxy-3-naphthoic acid, antipyrine complex of zinc thiocyanate, zinc of 2-acetyloxy-3-naphthoic acid Salts, 2-hydroxy-1-naphthoic acid, 1-hydroxy-2-naphthoic acid, metal salts of hydroxynaphthoic acid zinc, aluminum, calcium, etc., bis- (4-hydroxyphenyl) acetic acid methyl ester, bis- (4 -Hydroxyphenyl) acetic acid benzyl ester, 4- {β- (p-methoxyphenoxy) ethoxy } Salicylic acid, 1,3-bis (4-hydroxycumyl) benzene, 1,4-bis (4-hydroxycumyl) benzene, 2,4'-diphenolsulfone, 3,3'-diallyl-4,4 '-Diphenolsulfone, α, α-bis (4-hydroxyphenyl) -α-methyltoluene zinc antipyrine complex, tetrabromobisphenol A, tetrabromobisphenol S, 4,4'-thiobis (2-methylphenol) ), 3,4-dihydroxy-4'-methyl-diphenylsulfone, 4,4'-thiobis (2-chlorophenol), and the like. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular in the addition amount of the developer in a thermosensitive recording layer, According to the objective, it can select suitably, 1-20 weight part is preferable with respect to 1 weight part of leuco dye, and 2-10 weight part is more. preferable.

There is no restriction | limiting in particular as said binder resin, Although it can select suitably according to the objective from well-known things, For example, polyvinyl alcohol, starch or its derivative; methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, ethylcellulose Cellulose derivatives such as: polyacrylic acid soda, polyvinylpyrrolidone, acrylamide-acrylic acid ester copolymer, acrylamide-acrylic acid ester-methacrylic acid terpolymer, styrene-maleic anhydride copolymer alkali salt, isobutylene-anhydrous In addition to water-soluble polymers such as maleic acid copolymer alkali salts, polyacrylamide, sodium alginate, gelatin, casein, polyvinyl acetate, polyurethane, polyacrylic acid, polyacrylic acid Tellurium, polymethacrylic acid ester, polybutyl methacrylate, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, etc. emulsion; styrene-butadiene copolymer, latex such as styrene-butadiene-acrylic copolymer And the like.
These may be used individually by 1 type and may use 2 or more types together.

Various heat-fusible substances can be used as fillers in the heat-sensitive recording layer.
Specific examples of the heat-fusible substance include fatty acids such as stearic acid and behenic acid; fatty acid amides such as stearic acid amide and palmitic acid amide; zinc stearate, aluminum stearate, calcium stearate, zinc palmitate, behen Fatty acid metal salts such as zinc acid; p-benzylbiphenyl, terphenyl, triphenylmethane, benzyl p-benzyloxybenzoate, β-benzyloxynaphthalene, β-naphthoic acid phenyl ester, 1-hydroxy-2-naphthoic acid phenyl Ester, 1-hydroxy-2-naphthoic acid methyl ester, diphenyl carbonate, terephthalic acid dibenzyl ester, terephthalic acid dimethyl ester, 1,4-dimethoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dibenzyloxynaphtha 1,2-bis (phenoxy) ethane, 1,2-bis (3-methylphenoxy) ethane, 1,2-bis (4-methylphenoxy) ethane, 1,4-bis (phenoxy) butane, 1, 4-bis (phenoxy) -2-butene, 1,2-bis (4-methoxyphenylthio) ethane, dibenzoylmethane, 1,4-bis (phenylthio) butane, 1,4-bis (phenylthio) -2- Butene, 1,2-bis (4-methoxyphenylthio) ethane, 1,3-bis (2-vinyloxyethoxy) benzene, 1,4-bis (2-vinyloxyethoxy) benzene, p- (2-vinyl Oxyethoxy) biphenyl, p-aryloxybiphenyl, p-propargyloxybiphenyl, dibenzoyloxymethane, 1,3-dibenzoyloxypropane, di Disulfide, 1,1-diphenylethanol, 1,1-diphenylpropanol, p- (benzyloxy) benzyl alcohol, 1,3-diphenoxy-2-propanol, N-octadecylcarbamoyl-p-methoxycarbonylbenzene, N- Examples include octadecylcarbamoylbenzene, oxalic acid dibenzyl ester, 1,5-bis (p-methoxyphenyloxy) -3-oxapentane and the like.
These may be used individually by 1 type and may use 2 or more types together.

In the heat-sensitive recording layer, various auxiliary additive components such as a surfactant and a lubricant can be used in combination as other components as required. Examples of the lubricant include higher fatty acids or metal salts thereof, higher fatty acid amides, higher fatty acid esters, animal waxes, vegetable waxes, mineral waxes, petroleum waxes, and the like.
The method for forming the heat-sensitive recording layer is not particularly limited, and a generally known method can be adopted. For example, a leuco dye and a developer are separately provided together with a binder resin and other components, a ball mill, an attritor, and the like. After pulverizing and dispersing with a disperser such as a sand mill until the dispersed particle size becomes 1 to 3 μm, the mixture is mixed with a filler, a heat-fusible substance (sensitizer) dispersion liquid, etc., if necessary, in a predetermined formulation. A thermal recording layer coating solution may be prepared and coated on a support.
The thickness of the heat-sensitive recording layer varies depending on the composition of the heat-sensitive recording layer and the application of the heat-sensitive adhesive material, and cannot be specified unconditionally, but is preferably 1 to 50 μm, more preferably 3 to 20 μm.

-Protective layer-
The protective layer is preferably a material containing polyvinyl alcohol (PVAα) having a reactive carbonyl group and a hydrazide compound, and further containing other components as necessary.
A protective layer containing PVAα and a hydrazide compound as a cross-linking agent has extremely high heat resistance and water resistance, and is hardly affected by the addition of pressure, temperature, and humidity, so that the blocking resistance can be greatly improved.
PVAα can be produced by a known method such as saponification of a polymer obtained by copolymerizing a vinyl monomer having a reactive carbonyl group and a fatty acid vinyl ester.
Examples of the vinyl monomer having a reactive carbonyl group include a group having an ester residue and a group having an acetone group, but a vinyl monomer having a diacetone group is preferable, and specific examples include diacetone acrylamide and meta diacetone acrylamide. It is done. Examples of the fatty acid vinyl ester include vinyl formate, vinyl acetate, and vinyl propionate. Among these, vinyl acetate is particularly preferable.

PVAα may be a copolymer of other copolymerizable vinyl monomers. Examples of these copolymerizable vinyl monomers include acrylic acid esters, butadiene, ethylene, propylene, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and the like.
The content of the reactive carbonyl group in PVAα is preferably 0.5 to 20 mol% of the whole polymer, and more preferably in the range of 2 to 10 mol% in view of water resistance. If the content is less than 2 mol%, the practical water resistance is insufficient, and if it exceeds 10 mol%, no further improvement in water resistance is observed and the cost increases, which is not economical.
The polymerization degree of PVAα is preferably 300 to 3,000, more preferably 500 to 2,200. The saponification degree of PVAα is preferably 80% or more.

The hydrazide compound is not particularly limited as long as it has a hydrazide group, and can be appropriately selected according to the purpose. , Adipic acid dihydrazide, azelaic acid hydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, maleic acid dihydrazide, fumaric acid hydrazide, itaconic acid dihydrazide, benzoic acid hydrazide, glutaric acid dihydrazide, diglycolic acid hydrazide dihydrazide dihydric acid dihydrazide Examples thereof include isophthalic acid hydrazide, terephthalic acid dihydrazide, 2,7-naphthoic acid dihydrazide, and polyacrylic acid hydrazide. Among these, adipic acid dihydrazide is particularly preferable in terms of water resistance and safety.
These may be used individually by 1 type and may use 2 or more types together.
5-40 weight part is preferable with respect to 100 weight part of PVA (alpha), and, as for content of a hydrazide compound, 15-25 weight part is more preferable.

The protective layer preferably contains a filler.
The filler is not particularly limited and can be appropriately selected from known materials according to the purpose. For example, calcium carbonate, zinc oxide, aluminum oxide, titanium dioxide, silica, aluminum hydroxide, barium sulfate, talc, kaolin, Examples thereof include inorganic pigments such as alumina, clay and alkaline silicic acids, or known organic pigments.
Among these, in consideration of matching with the thermal head (deposition adhesion) and the like, basic hydroxides such as aluminum hydroxide and calcium carbonate are preferable. Furthermore, aluminum hydroxide is particularly preferable in consideration of pH control due to moderate water solubility.
In view of water resistance (water peeling resistance), silica, kaolin and alumina which are acidic pigments (showing acidity in an aqueous solution) are preferable, and silica is particularly preferable from the viewpoint of color density.
The method for forming the protective layer is not particularly limited, and a generally known method can be adopted. For example, a protective layer coating solution may be prepared by a conventional method and coated on the heat-sensitive recording layer.
There is no restriction | limiting in particular in the thickness of a protective layer, Although it can select suitably according to the objective, 1.0-7.0 micrometers is preferable.

If necessary, an intermediate layer can be further provided between the support and the heat-sensitive recording layer.
As the component constituting the intermediate layer, the aforementioned filler, binder resin, heat fusible substance, surfactant and the like can be used.
The heat-sensitive adhesive material of the present invention may be cut and used before or after thermal activation (heating) of the heat-sensitive adhesive layer. Therefore, it is preferable to form a cut in the heat-sensitive adhesive material in advance because the heat-sensitive adhesive material can be suitably used for various uses such as labels and tags.
There is no restriction | limiting in particular in the shape of the heat-sensitive adhesive material of this invention, A label form, a sheet form, a label sheet form, a roll form etc. are mentioned. Among these, a roll shape wound around a cylindrical core material is particularly preferable from the viewpoint of convenience, storage location, and handleability.

There are no particular restrictions on the adherend to which the heat-sensitive adhesive material of the present invention is applied, and the size, shape, structure, material, etc. can be appropriately selected according to the purpose. (For example, polyethylene, polypropylene, etc.), resin plates such as acrylic, polyethylene terephthalate (PET), polystyrene, nylon, etc .; metal plates, such as SUS, aluminum; paper products such as envelopes, cardboard, etc .; polyolefin wraps; Wraps, polyethylene nonwoven fabrics (envelopes, etc.) and the like.
In particular, the heat-sensitive adhesive material of the present invention has a great feature in that it has a strong adhesive force to rough adherends such as corrugated cardboard as compared to conventional ones, and can be firmly attached. It is advantageous to use it.
The method for thermally activating the heat-sensitive adhesive layer of the heat-sensitive adhesive material of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an activation method using hot air or a hot roll is used. Examples include an activation method and an activation method using a thermal head. Among these, the thermal head activation method uses the existing thermal recording printer device to heat both sides of the thermal adhesive material, thereby recording on the thermal recording layer and thermal activation of the thermal adhesive layer. Are particularly preferred because they can be carried out simultaneously.

  According to the present invention, the adhesive strength in a wide temperature environment from low temperature (0 ° C.) to high temperature (40 ° C.) is strong particularly on rough surface adherends such as corrugated cardboard, and the adhesive strength decreases with time. It is possible to provide a heat-sensitive adhesive material that can be thermally activated at low energy by a thermal head and has good blocking resistance.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited at all by these Examples. “Parts” and “%” are both “parts by weight” and “% by weight”.

(Preparation Example 1-1)
-Preparation of under layer coating solution [A-1 solution]-
A mixture having the following composition was stirred and dispersed to prepare an under layer coating solution [A-1 solution].
・ Plastic spherical hollow particles (copolymer resin mainly composed of vinylidene chloride-acrylonitrile, solid content concentration 32%, volume average particle diameter 3.0 μm, hollow ratio 92%) ... 15 parts ・ Styrene-butadiene copolymer latex (Tg4 ℃, Nippon A & L Co., Ltd. Smartex PA-9159) ... 10 parts · Water ... 60 parts

(Preparation Example 1-2)
-Preparation of under layer coating solution [A-2 solution]-
A mixture having the following composition was stirred and dispersed to prepare an under layer coating solution [A-2 solution].
・ Plastic spherical hollow particles (copolymer resin mainly composed of vinylidene chloride-acrylonitrile, solid content concentration 32%, volume average particle diameter 3.0 μm, hollow rate 92%) ... 15 parts ・ Carboxy-modified styrene-butadiene copolymer latex (Tg-34 ° C., NALSTAR SR-111 manufactured by Nippon A & L Co., Ltd.)… 10 parts ・ Water… 60 parts

(Preparation Example 1-3)
-Preparation of under layer coating solution [A-3 solution]-
A mixture having the following composition was stirred and dispersed to prepare an under layer coating solution [A-3 solution].
・ Plastic spherical hollow particles (copolymer resin mainly composed of vinylidene chloride-acrylonitrile, solid content concentration 32%, volume average particle diameter 3.0 μm, hollow rate 92%) ... 15 parts ・ Carboxy-modified styrene-butadiene copolymer latex (Tg 25 ° C, NALSTAR SR-100 manufactured by Nippon A & L Co., Ltd.) ... 10 parts ・ Water ... 60 parts

(Preparation Example 1-4)
-Preparation of under layer coating solution [A-4 solution]-
A mixture having the following composition was stirred and dispersed to prepare an under layer coating solution [A-4 solution].
・ Plastic spherical hollow particles (copolymer resin mainly composed of vinylidene chloride-acrylonitrile, solid content concentration 32%, volume average particle diameter 3.0 μm, hollow rate 92%) ... 15 parts ・ Carboxy-modified styrene-butadiene copolymer latex (Tg35 ° C, NALSTAR SR-143 manufactured by Nippon A & L Co., Ltd.) ... 10 parts ・ Water ... 60 parts

(Preparation Example 1-5)
-Preparation of under layer coating solution [A-5 solution]-
A mixture having the following composition was stirred and dispersed to prepare an under layer coating solution [A-5 solution].
・ Plastic spherical hollow particles (copolymer resin mainly composed of vinylidene chloride-acrylonitrile, solid content concentration 32%, volume average particle diameter 3.0 μm, hollow rate 92%) ... 15 parts ・ Carboxy-modified styrene-butadiene copolymer latex (Tg-42 ° C, Nalstar SR-112, manufactured by Nippon A & L Co., Ltd.) ... 10 parts ・ Water: 60 parts

(Preparation Example 1-6)
-Preparation of under layer coating solution [A-6 solution]-
A mixture having the following composition was stirred and dispersed to prepare an under layer coating solution [A-6 solution].
・ Plastic spherical hollow particles (acrylonitrile-vinylidene chloride-methyl methacrylate copolymer, solid content concentration 41%, volume average particle diameter 3.2 μm, hollow ratio 70%) 11 parts ・ Styrene-butadiene copolymer latex (Tg4 ℃, Nippon A & L Co., Ltd. Smartex PA-9159) ... 10 parts · Water ... 60 parts

(Preparation Example 1-7)
-Preparation of under layer coating solution [A-7 solution]-
A mixture having the following composition was stirred and dispersed to prepare an under layer coating solution [A-7 solution].
・ Plastic spherical hollow particles (acrylonitrile-vinylidene chloride-methyl methacrylate copolymer, solid concentration 40%, volume average particle diameter 1.5 μm, hollow ratio 50%) 15 parts ・ Styrene-butadiene copolymer latex (Tg4 ℃, Nippon A & L Co., Ltd. Smartex PA-9159) ... 10 parts · Water ... 60 parts

(Preparation Example 1-8)
-Preparation of under layer coating solution [A-8 solution]-
A mixture having the following composition was stirred and dispersed to prepare an under layer coating solution [A-8 solution].
Plastic spherical hollow particles (acrylonitrile-methacrylonitrile-isobornyl methacrylate copolymer, solid content concentration 33%, volume average particle diameter 6.0 μm, hollow ratio 91%)
... 13.7 parts-Styrene-butadiene copolymer latex (Tg 4 ° C, SMARTEX PA-9159 manufactured by Nippon A & L Co., Ltd.) ... 10 parts-Water ... 60 parts

(Preparation Example 1-9)
-Preparation of under layer coating solution [A-9 solution]-
A mixture having the following composition was stirred and dispersed to prepare an under layer coating solution [A-9 solution].
・ Plastic spherical hollow particles (copolymer resin mainly composed of vinylidene chloride-acrylonitrile, solid content concentration 32%, volume average particle diameter 3.0 μm, hollow ratio 92%)... 3.1 parts ・ Styrene-butadiene copolymer latex (Tg 4 ° C, Nippon A & L, Smartex PA-9159) ... 11 parts Water ... 60 parts

(Preparation Example 1-10)
-Preparation of under layer coating solution [A-10 solution]-
A mixture having the following composition was stirred and dispersed to prepare an underlayer coating solution [A-10 solution].
・ Plastic spherical hollow particles (copolymer resin mainly composed of vinylidene chloride-acrylonitrile, solid content concentration 32%, volume average particle diameter 3.0 μm, hollow rate 92%) 34.3 parts ・ Styrene-butadiene copolymer latex (Tg 4 ° C., SMARTEX PA-9159 manufactured by Nippon A & L Co., Ltd.)… 10 parts ・ Water… 60 parts

(Preparation Example 1-11)
-Preparation of under layer coating solution [A-11 solution]-
A mixture having the following composition was stirred and dispersed to prepare an under layer coating solution [A-11 solution].
・ Plastic spherical hollow particles (copolymer resin mainly composed of vinylidene chloride-acrylonitrile, solid content concentration 32%, volume average particle diameter 3.0 μm, hollow ratio 92%) 33.4 parts ・ Acrylate ester copolymer aqueous Emulsion (Tg-65 ° C., solid content concentration 55%,
Showa High Polymer Co., Ltd., Polysol PSA SE-4040) ... 16.3 parts Water: 60 parts

(Preparation Example 2-1)
-Preparation of Hot Melt Substance Dispersion [Liquid B-1]-
A mixture having the following composition was dispersed with a sand mill so that the volume average particle diameter was 1.0 μm to prepare a hot melt material dispersion [B-1 solution].
Triphenylphosphine 30.0 parts Polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Gocelan L-3266,
10 parts aqueous solution) ... 15 parts Surfactant (manufactured by Nippon Emulsifier Co., Ltd., Newcol 290M, 10% aqueous solution) ... 1.5 partsWater: 53.5 parts

(Preparation Example 2-2-1)
-Preparation of Hot Melt Material Dispersion Liquid [C-1-1 Liquid]-
A mixture having the following composition was dispersed with a sand mill so that the volume average particle diameter was 1.0 μm to prepare a hot melt substance dispersion [C-1-1].
・ 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole (melting point: 138 ° C.) 30.0 parts ・ Polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Goceran L-3266,
10 parts aqueous solution) ... 15 parts Surfactant (manufactured by Nippon Emulsifier Co., Ltd., Newcol 290M, 10% aqueous solution) ... 1.5 partsWater: 53.5 parts

(Preparation Example 2-2-2)
-Preparation of Hot Melt Substance Dispersion Liquid [C-1-2 Liquid]-
A mixture having the following composition was dispersed with a sand mill so that the volume average particle diameter was 1.0 μm to prepare a hot melt material dispersion [C-1-2 solution].
2- (2′-hydroxy-3 ′, 5′-t-butylphenyl) -5-chlorobenzotriazole (melting point 152 ° C.) 30.0 parts Polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Goceran L-3266) ,
10% aqueous solution) ... 15 parts Surfactant (Nippon Emulsifier, Newcol 290M, 10% aqueous solution ... 1.5 parts) Water ... 53.5 parts

(Preparation Example 2-2-3)
—Preparation of Hot Melt Substance Dispersion Liquid [C-1-3 Liquid] —
A mixture having the following composition was dispersed with a sand mill so that the volume average particle diameter was 1.0 μm to prepare a hot melt material dispersion [C-1-3 liquid].
2- [2'-hydroxy-3 ', 5'-di (1,1-dimethylbenzyl) phenyl]
Benzotriazole (melting point 140 ° C.) 30.0 parts Polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Gocelan L-3266,
10 parts aqueous solution) ... 15 parts Surfactant (manufactured by Nippon Emulsifier Co., Ltd., Newcol 290M, 10% aqueous solution) ... 1.5 partsWater: 53.5 parts

(Preparation Example 2-2-4)
-Preparation of Hot Melt Substance Dispersion [C-1-4 Solution]-
A mixture having the following composition was dispersed with a sand mill so that the volume average particle diameter was 1.0 μm to prepare a hot melt material dispersion [C-1-4 solution].
2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole (melting point: 102 ° C.) 30.0 parts Polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Goceran L-3266,
10 parts aqueous solution) ... 15 parts Surfactant (Nippon Emulsifier, Newcol 290M, 10% aqueous solution)
… 1.5 parts ・ Water… 53.5 parts

(Preparation Example 2-3)
-Preparation of silicone resin dispersion [D-1 solution]-
A mixture having the following composition was dispersed using a sand mill so that the volume average particle size was 1.0 μm to obtain a dispersion [D-1 solution].
Silicone resin resin particles (manufactured by Shin-Etsu Chemical Co., KMP-590) 30.0 parts Polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Goceran L-3266,
30% aqueous solution) ... 5.0 parts Surfactant (manufactured by Nippon Emulsifier, Newcol 290M, 10% aqueous solution) ... 1.5 parts Water: 64.85 parts

(Preparation Example 3-1-1)
-Preparation of heat-sensitive adhesive coating solution [E-1-1 solution]-
A mixture having the following composition was uniformly mixed to prepare a heat-sensitive adhesive coating solution [E-1-1 solution].
-Acrylate ester copolymer aqueous emulsion (Tg-65 ° C, solid content concentration 55%,
Showa High Polymer Co., Ltd., Polysol PSA SE-4040) ... 9.2 parts Tackifier (terpene phenol main component, Arakawa Chemical Co., Ltd., E-100, solid content concentration 50%, softening point 150 [deg.] C.) ... 6. 6 parts-Hot melt substance dispersion [B-1 liquid] ... 71.7 parts-Hot melt substance dispersion [C-1-1 liquid] ... 12.6 parts-Silicone resin dispersion [D-1 liquid] ... 3.8 parts

(Preparation Example 3-1-2)
-Preparation of thermosensitive adhesive coating solution [E-1-2 solution]-
A mixture having the following composition was uniformly mixed to prepare a heat-sensitive adhesive coating solution [E-1-2 solution].
-Acrylate ester copolymer aqueous emulsion (Tg-65 ° C, solid content concentration 55%,
Showa High Polymer Co., Ltd., Polysol PSA SE-4040) ... 9.2 parts Tackifier (terpene phenol main component, Arakawa Chemical Co., Ltd., E-100, solid content concentration 50%, softening point 150 [deg.] C.) ... 6. 6 parts-Hot melt substance dispersion (B-1 liquid) ... 63.2 parts-Hot melt substance dispersion (C-1-2 liquid) ... 21.1 parts-Silicone resin dispersion (D-1 liquid) ... 3.8 parts

(Preparation Example 3-1-3)
-Preparation of thermosensitive adhesive coating solution [E-1-3 solution]-
A mixture having the following composition was uniformly mixed to prepare a heat-sensitive adhesive coating solution [E-1-3 solution].
-Acrylate ester copolymer aqueous emulsion (Tg-65 ° C, solid content concentration 55%,
Showa High Polymer Co., Ltd., Polysol PSA SE-4040) ... 9.2 parts Tackifier (terpene phenol main component, Arakawa Chemical Co., Ltd., E-100, solid content concentration 50%, softening point 150 [deg.] C.) ... 6. 6 parts-Hot melt substance dispersion (B-1 liquid) ... 63.2 parts-Hot melt substance dispersion (C-1-3 liquid) ... 21.1 parts-Silicone resin dispersion (D-1 liquid) ... 3.8 parts

(Preparation Example 3-2)
-Preparation of thermosensitive adhesive coating solution [E-2 solution]-
A mixture having the following composition was uniformly mixed to prepare a heat-sensitive adhesive coating solution [E-2 solution].
-Acrylate ester copolymer aqueous emulsion (Tg-65 ° C, solid content concentration 55%,
Showa High Polymer Co., Ltd., Polysol PSA SE-4040) ... 9.2 parts Tackifier (terpene phenol main component, Arakawa Chemical Co., Ltd., E-100, solid content concentration 50%, softening point 150 [deg.] C.) ... 6. 6 parts-Hot melt substance dispersion (B-1 liquid) ... 63.2 parts-Hot melt substance dispersion (C-1-1 liquid) ... 21.1 parts-Silicone resin dispersion (D-1 liquid) ... 3.8 parts

(Preparation Example 3-3)
-Preparation of thermosensitive adhesive coating solution [E-3 solution]-
A mixture having the following composition was uniformly mixed to prepare a heat-sensitive adhesive coating solution [E-3 solution].
-Acrylate ester copolymer aqueous emulsion (Tg-65 ° C, solid content concentration 55%,
Showa High Polymer Co., Ltd., Polysol PSA SE-4040) ... 9.2 parts Tackifier (terpene phenol main component, Arakawa Chemical Co., Ltd., E-100, solid content concentration 50%, softening point 150 [deg.] C.) ... 6. 6 parts-Hot melt substance dispersion (B-1 liquid) ... 67.44 parts-Hot melt substance dispersion (C-1-1 liquid) ... 16.86 parts-Silicone resin dispersion (D-1 liquid) ... 3.8 parts

(Preparation Example 3-4)
-Preparation of thermosensitive adhesive coating solution [E-4 solution]-
A mixture having the following composition was uniformly mixed to prepare a heat-sensitive adhesive coating solution [E-4 solution].
-Acrylate ester copolymer aqueous emulsion (Tg-65 ° C, solid content concentration 55%,
Showa High Polymer Co., Ltd., Polysol PSA SE-4040) ... 9.2 parts Tackifier (terpene phenol main component, Arakawa Chemical Co., Ltd., E-100, solid content concentration 50%, softening point 150 [deg.] C.) ... 6. 6 parts-Hot melt substance dispersion (B-1 liquid) ... 75.87 parts-Hot melt substance dispersion (C-1-1 liquid) ... 8.43 parts-Silicone resin dispersion (D-1 liquid) ... 3.8 parts

(Preparation Example 3-5)
-Preparation of thermosensitive adhesive coating solution [E-5 solution]-
A mixture having the following composition was uniformly mixed to prepare a heat-sensitive adhesive coating solution [E-5 solution].
-Acrylate ester copolymer aqueous emulsion (Tg-65 ° C, solid content concentration 55%,
Showa High Polymer Co., Ltd., Polysol PSA SE-4040) ... 9.2 parts Tackifier (terpene phenol main component, Arakawa Chemical Co., Ltd., E-100, solid content concentration 50%, softening point 150 [deg.] C.) ... 6. 6 parts-Hot melt substance dispersion (B-1 liquid) ... 80.08 parts-Hot melt substance dispersion (C-1-1 liquid) ... 4.22 parts-Silicone resin dispersion (D-1 liquid) ... 3.8 parts

(Preparation Example 3-6)
-Preparation of thermosensitive adhesive coating solution [E-6 solution]-
A mixture having the following composition was uniformly mixed to prepare a heat-sensitive adhesive coating solution [E-6 solution].
-Acrylate ester copolymer aqueous emulsion (Tg-65 ° C, solid content concentration 55%,
Showa High Polymer Co., Ltd., Polysol PSA SE-4040) ... 9.2 parts Tackifier (terpene phenol main component, Arakawa Chemical Co., Ltd., E-100, solid content concentration 50%, softening point 150 [deg.] C.) ... 6. 6 parts-Hot melt substance dispersion [B-1 liquid] ... 80.08 parts-Hot melt substance dispersion (C-1-1 liquid) ... 4.22 parts

(Preparation Example 3-7)
-Preparation of thermosensitive adhesive coating solution [E-7 solution]-
A mixture having the following composition was uniformly mixed to prepare a heat-sensitive adhesive coating solution [E-7 solution].
-Acrylate ester copolymer aqueous emulsion (Tg-65 ° C, solid content concentration 55%,
Showa High Polymer Co., Ltd., Polysol PSA SE-4040) ... 9.2 parts Tackifier (terpene phenol main component, Arakawa Chemical Co., Ltd., E-100, solid content concentration 50%, softening point 150 [deg.] C.) ... 6. 6 parts ・ Hot-melting substance dispersion (B-1 liquid) ... 84.2 parts

(Preparation Example 3-8)
-Preparation of thermosensitive adhesive coating solution [E-8 solution]-
A mixture having the following composition was uniformly mixed to prepare a heat-sensitive adhesive coating solution [E-8 solution].
-Acrylate ester copolymer aqueous emulsion (Tg-65 ° C, solid content concentration 55%,
Showa High Polymer Co., Ltd., Polysol PSA SE-4040) ... 9.2 parts Tackifier (terpene phenol main component, Arakawa Chemical Co., Ltd., E-100, solid content concentration 50%, softening point 150 [deg.] C.) ... 6. 6 parts-Hot melt substance dispersion (C-1-1 liquid) ... 84.2 parts

(Example 1-1)
-Production of heat-sensitive adhesive material-
^On the side of the single-side coated paper (OK Adonis Rough, manufactured by Oji Paper Co., Ltd.) having a basis weight of 80 g / m ² as the support, the under layer coating solution [A-1] is dried at 5 g / The under layer was formed by applying and drying to m ² .
On the obtained under layer, the heat-sensitive adhesive layer coating solution [E-1-1 solution] was applied and dried so that the dry adhesion amount was 10 g / m ² to form a heat-sensitive adhesive layer.
Thus, the heat-sensitive adhesive material of Example 1-1 was produced.

(Example 1-2)
-Production of heat-sensitive adhesive material-
Example 1 is the same as Example 1-1 except that the heat-sensitive adhesive layer coating solution [E-1-1 solution] is changed to a heat-sensitive adhesive layer coating solution [E-1-2 solution]. -2 heat-sensitive adhesive material was produced.

(Example 1-3)
-Production of heat-sensitive adhesive material-
Example 1 was performed in the same manner as Example 1-1 except that the heat-sensitive adhesive layer coating solution [E-1-1 solution] was changed to a heat-sensitive adhesive layer coating solution [E-1-3 solution]. -3 heat-sensitive adhesive material was produced.

(Example 2)
-Production of heat-sensitive adhesive material-
A thermosensitive adhesive material of Example 2 was produced in the same manner as Example 1-1 except that the under layer coating solution [A-1 solution] was changed to the under layer coating solution [A-2 solution]. .

(Example 3)
-Production of heat-sensitive adhesive material-
A thermosensitive adhesive material of Example 3 was produced in the same manner as Example 1-1 except that the under layer coating solution [A-1 solution] was changed to the under layer coating solution [A-3 solution]. .

Example 4
-Production of heat-sensitive adhesive material-
A heat-sensitive adhesive material of Example 4 was produced in the same manner as Example 1-1 except that the under layer coating solution [A-1 solution] was changed to the under layer coating solution [A-6 solution]. .

(Example 5)
-Production of heat-sensitive adhesive material-
A thermosensitive adhesive material of Example 5 was produced in the same manner as Example 1-1 except that the under layer coating solution [A-1 solution] was changed to the under layer coating solution [A-7 solution]. .

(Example 6)
-Production of heat-sensitive adhesive material-
A heat-sensitive adhesive material of Example 6 was produced in the same manner as Example 1-1 except that the under layer coating solution [A-1 solution] was changed to the under layer coating solution [A-8 solution]. .

(Example 7)
-Production of heat-sensitive adhesive material-
A thermosensitive adhesive material of Example 7 was produced in the same manner as Example 1-1 except that the under layer coating solution [A-1 solution] was changed to the under layer coating solution [A-9 solution]. .

(Example 8)
-Production of heat-sensitive adhesive material-
A thermosensitive adhesive material of Example 8 was produced in the same manner as Example 1-1 except that the under layer coating solution [A-1 solution] was changed to the under layer coating solution [A-10 solution]. .

Example 9
-Production of heat-sensitive adhesive material-
Except that the heat-sensitive adhesive layer coating solution [E-1-1] was applied so that the dry adhesion amount was 8 g / m ² and dried to form a heat-sensitive adhesive layer, Example 1-1 and Similarly, the heat-sensitive adhesive material of Example 9 was produced.

(Example 10)
-Production of heat-sensitive adhesive material-
Example 1-1, except that the heat-sensitive adhesive layer coating solution [E-1-1 solution] was applied so as to have a dry adhesion amount of 20 g / m ² and dried to form a heat-sensitive adhesive layer. In the same manner as described above, a heat-sensitive adhesive material of Example 10 was produced.

(Example 11)
-Production of heat-sensitive adhesive material-
Example 1-1, except that the heat-sensitive adhesive layer coating solution [E-1-1 solution] was applied so that the dry adhesion amount was 25 g / m ² and dried to form a heat-sensitive adhesive layer. In the same manner, a heat-sensitive adhesive material of Example 11 was produced.

(Example 12)
-Production of heat-sensitive adhesive material-
Example 12 was carried out in the same manner as Example 1-1, except that the heat-sensitive adhesive layer coating solution [E-1-1 solution] was changed to a heat-sensitive adhesive layer coating solution [E-2 solution]. A heat-sensitive adhesive material was prepared.

(Example 13)
-Production of heat-sensitive adhesive material-
Example 13 was carried out in the same manner as Example 1-1 except that the heat-sensitive adhesive layer coating solution [E-1-1 solution] was changed to a heat-sensitive adhesive layer coating solution [E-3 solution]. A heat-sensitive adhesive material was prepared.

(Example 14)
-Production of heat-sensitive adhesive material-
Example 14 was carried out in the same manner as Example 1-1 except that the heat-sensitive adhesive layer coating solution [E-1-1 solution] was changed to a heat-sensitive adhesive layer coating solution [E-4 solution]. A heat-sensitive adhesive material was prepared.

(Example 15)
-Production of heat-sensitive adhesive material-
Example 15 was carried out in the same manner as Example 1-1 except that the heat-sensitive adhesive layer coating solution [E-1-1 solution] was changed to a heat-sensitive adhesive layer coating solution [E-5 solution]. A heat-sensitive adhesive material was prepared.

(Example 16)
<Formation of thermal recording layer>
-Preparation of non-foaming heat insulating layer forming coating solution [F solution]-
A mixture having the following composition was stirred and dispersed to prepare a non-foaming heat insulating layer forming coating solution [F solution].
・ Small hollow particle dispersion (copolymer resin mainly composed of vinylidene chloride-acrylonitrile, solid content concentration 32%, volume average particle diameter 3.6 μm, hollow ratio 92%)... 30 parts ・ Styrene-butadiene copolymer latex ( Tg 4 ° C., SMARTEX PA-9159 manufactured by Nippon A & L Co., Ltd.) ... 10 parts Surfactant (Dapro W-77 manufactured by Elementis Japan Co., Ltd.) 0.1 part Water 60 parts

-Preparation of color former dispersion [liquid G]-
A color developing agent dispersion [liquid G] was prepared by stirring and dispersing a mixture having the following composition.
-3-di-n-butylamino-6-methyl-7-anilinofluorane ... 20 parts-Polyvinyl alcohol (Nippon Gosei Chemical Industry Co., Ltd., Goceran L-3266,
10% aqueous solution)… 10 parts ・ Water… 70 parts

-Preparation of developer dispersion [liquid H]-
A developer having the following composition was dispersed with a sand mill so that the volume average particle diameter was 1.5 μm, respectively, to prepare a developer dispersion [Liquid H].
4-isopropoxy-4'-hydroxydiphenyl sulfone: 10 parts Polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Goceran L-3266,
10% aqueous solution) ... 25 parts Calcium carbonate (Shiraishi Kogyo Co., Ltd., CALSITEC Brilliant-15
... 15 parts ・ Water ... 50 parts

Next, color developer dispersion [liquid G]: developer dispersion [liquid H] = 1: 8 (weight ratio) are mixed and stirred to prepare a heat-sensitive color developing layer coating liquid [liquid I]. did.
Next, the non-foaming heat insulating layer forming coating solution [F solution] is dried on the surface of single-sided coated paper (OK Adonis Rough, manufactured by Oji Paper Co., Ltd.) having an average basis weight of 80 g / m ² , and the weight after drying is 4 g / m ^2. It was applied and dried so that a non-foaming heat insulating layer was provided.
Next, the color former dispersion liquid [G liquid] was applied onto the non-foaming heat insulating layer after drying so as to have a weight of 5 g / m ² and dried to provide a heat-sensitive recording layer. Thereafter, a super-calender treatment was performed so that the Oken type smoothness was 2,000 seconds to prepare a thermal recording paper having a thermal recording layer.
Next, the under layer coating solution [A-1] is applied on the support surface on the side having no heat-sensitive recording layer of the obtained heat-sensitive recording paper so that the dry adhesion amount is 5 g / m ² and dried. An under layer is formed, and a heat-sensitive adhesive layer coating solution [E-1-1 solution] is applied on the under layer so that the dry adhesion amount is 10 g / m ² and dried to form a heat-sensitive adhesive layer. did.
As described above, the heat-sensitive adhesive material of Example 16 was produced.

(Comparative Example 1)
-Production of heat-sensitive adhesive material-
The under layer coating solution [A-11 solution] is applied to the surface of the single-sided coated paper (OK Adonis Rough, manufactured by Oji Paper Co., Ltd.) having a basis weight of 80 g / m ² as a support on the side having no coating layer. The underlayer was formed by applying and drying at 5 g / m ² .
On this under layer, the heat-sensitive adhesive layer coating liquid [E-7 liquid] was applied and dried so that the dry adhesion amount was 10 g / m ² to form a heat-sensitive adhesive layer.

(Comparative Example 2)
-Production of heat-sensitive adhesive material-
The under layer coating solution [A-11 solution] is applied to the surface of the single-sided coated paper (OK Adonis Rough, manufactured by Oji Paper Co., Ltd.) having a basis weight of 80 g / m ² as a support on the side having no coating layer. The underlayer was formed by applying and drying at 5 g / m 2. On this under layer, a heat-sensitive adhesive layer coating solution [E-8 solution] was applied and dried so as to have a dry adhesion amount of 10 g / m ² to form a heat-sensitive adhesive layer.
Thus, the heat-sensitive adhesive material of Comparative Example 2 was produced.

(Comparative Example 3)
-Production of heat-sensitive adhesive material-
The underlayer coating solution [A-4 solution] was applied and dried so that the dry adhesion amount was 5 g / m ^2, and was the same as Example 1-1 except that a heat-sensitive adhesive layer was formed. Thus, a heat-sensitive adhesive material of Comparative Example 3 was produced.

(Comparative Example 4)
-Production of heat-sensitive adhesive material-
The under layer coating solution [A-5 solution] was applied and dried so that the dry adhesion amount was 5 g / m ^2, and the same procedure as in Example 1-1 was performed except that a heat-sensitive adhesive layer was formed. Thus, a heat-sensitive adhesive material of Comparative Example 4 was produced.

(Comparative Example 5)
-Production of heat-sensitive adhesive material-
A heat-sensitive adhesive material of Comparative Example 5 was produced in the same manner as Example 1-1 except that no underlayer was formed.

(Comparative Example 6)
-Production of heat-sensitive adhesive material-
A heat-sensitive adhesive material of Comparative Example 6 was produced in the same manner as in Example 1-1 except that the under layer coating solution [A-1 solution] was changed to the under layer coating solution [A-11 solution]. .

(Comparative Example 7)
-Production of heat-sensitive adhesive material-
Comparative Example 7 was performed in the same manner as Example 1-1 except that the heat-sensitive adhesive layer coating solution [E-1-1 solution] was changed to a heat-sensitive adhesive layer coating solution [E-8 solution]. A heat-sensitive adhesive material was prepared.

(Comparative Example 8)
-Production of heat-sensitive adhesive material-
Comparative Example 8 was conducted in the same manner as Example 1-1 except that the heat-sensitive adhesive layer coating solution [E-1-1 solution] was changed to a heat-sensitive adhesive layer coating solution [E-6 solution]. A heat-sensitive adhesive material was prepared.

Comparative Example 9
Comparative Example 9 was carried out in the same manner as Example 1-1 except that the heat-sensitive adhesive layer coating solution [E-1-1 solution] was changed to a heat-sensitive adhesive layer coating solution [E-7 solution]. A heat-sensitive adhesive material was prepared.

Next, the adhesive strength and blocking resistance of the obtained heat-sensitive adhesive materials of Examples 1-1 to 17 and Comparative Examples 1 to 7 were evaluated as follows. The results are shown in Table 2.
<Adhesion measurement>
Each heat-sensitive adhesive material was cut into a 25 mm × 150 mm rectangle, and using a thermal printing apparatus (manufactured by Okura Electric Co., Ltd., TH-PMD), head conditions: energy 0.5 mJ / dot, printing speed: 4 ms / line, platen Pressure: Thermally activated under the condition of 6 kgf / line. Subsequently, it was attached to the adherend (cardboard) in the longitudinal direction with a rubber roller of 2 kg under pressure, and after 2 minutes and 1 day, it was peeled off under the conditions of a peeling angle of 180 degrees and a peeling speed of 300 mm / min.
The adhesive strength at that time was measured with a force gauge (MODEL DPS-5, manufactured by IMADA), and the data was read and averaged at intervals of 0.1 seconds to show the numerical values. The unit is gf / 25 mm. This test was performed under a low temperature environment (0 ° C.), a normal temperature and humidity environment (23 ° C., 65% RH), and a high temperature environment (40 ° C., 60% RH).
[Evaluation criteria for adhesion to cardboard]
The evaluation criteria for adhesive strength shown in Table 2 are as follows.
A: 700 gf / 25 mm or more
○: 500 gf / 25 mm or more and less than 700 gf / 25 mm
Δ: 300 gf / 25 mm or more and less than 500 gf / 25 mm
X: Less than 300 gf / 25 mm

<Evaluation of blocking resistance>
The surface opposite to the heat-sensitive adhesive layer surface (heat-sensitive recording layer) of each heat-sensitive adhesive material was brought into contact, applied with a pressure of 200 gf / cm ² , and allowed to stand for 24 hours at 50 ° C. under Dry conditions. Next, after leaving at room temperature, the sample was peeled off, and the blocking resistance at that time was evaluated according to the criteria shown in Table 1 below. The ranks are divided into 10 ranks, with ranks 10 and 9 being “◎”, ranks 8 and 7 being “◯”, ranks 6, 5, and 4 being “Δ”, and ranks 3, 2, and 1 being “x”. Rank 7 or higher is a practical level. The evaluation results are shown in Table 2.
In addition, it refers to the state in which the degree of blocking becomes heavier in the order of “resistance feeling at peeling”, “peeling sound”, “spot transfer”, “peeling”, and “resistance feeling at peeling” refers to adhesiveness. It means that it sticks lightly even when it is not held, and the “self-weight” in it means a state where even if it sticks lightly, it will peel off naturally if you hold only the top two sheets of paper. Also, “peeling sound” means that a sound is produced when it is peeled from a sticky state, and “spot transfer” is a state in which the heat-sensitive adhesive layer is transferred to the back surface in a point shape. "Hagare" is a phenomenon in which the heat-sensitive adhesive layer sticks to the back surface and the heat-sensitive adhesive layer peels off or the paper on the back surface peels (breaks). Refers to that.

From the results shown in Table 2, Examples 1-1 to 17 have stronger adhesive strength in a low temperature (0 ° C.) to high temperature (40 ° C.) environment with respect to corrugated cardboard than Comparative Examples 1 to 7, and adhesion over time. It was confirmed that thermal activation with low energy was possible with a thermal head and that blocking resistance was good.
Moreover, since the thermoplastic resin was richer in Example 7 than the hollow filler in the under layer, the blocking property was slightly lowered.
In Example 8, since the hollow filler was richer than the thermoplastic resin in the under layer, the binding force of the under layer was weakened, and the adhesive strength at low and normal temperatures was slightly reduced.
In Example 9, since the dry adhesion amount of the heat-sensitive adhesive layer was outside the lower limit of the preferred range, the adhesive force at low temperature (0 ° C.) to high temperature (40 ° C.) was slightly weakened.
In Example 11, since the dry adhesion amount of the heat-sensitive adhesive layer was outside the upper limit of the preferable range, the heat insulating effect of the under layer was weakened and the adhesive force was slightly reduced.
In Example 12, since the content of triphenylphosphine in the hot-melt material was outside the lower limit of the preferred range, the adhesive force immediately after pasting at 23 ° C. to 40 ° C. was slightly reduced.
In Example 15, since the content of triphenylphosphine in the hot-melt material was outside the upper limit of the preferred range, the adhesive strength and blocking resistance were slightly lowered.
In Examples 1-1 to 6, 10, and 13 to 14, the content of triphenylphosphine in the hot-melt material is 80 to 90%. The blocking resistance was also excellent.

Since Comparative Example 1 uses only triphenylphosphine as the hot-melt material of the heat-sensitive adhesive layer and does not use a styrene-butadiene copolymer or a carboxy-modified styrene-butadiene copolymer as the thermoplastic resin of the under layer, The adhesive strength was extremely weak and the blocking property was extremely poor.
Comparative Example 2 uses only benzotriazole as the hot-melt material of the heat-sensitive adhesive layer, and does not use styrene-butadiene copolymer or carboxy-modified styrene-butadiene copolymer as the thermoplastic resin of the under layer. The adhesive strength was extremely inferior.
In Comparative Example 3, since the glass transition temperature of the thermoplastic resin in the under layer was 35 ° C., the adhesive strength at low temperature was extremely inferior.
In Comparative Example 4, since the glass transition temperature of the thermoplastic resin in the under layer was −42 ° C., the blocking property was inferior.
Since Comparative Example 5 did not have an under layer, the adhesive strength at low temperatures was extremely poor.
Since the comparative example 6 did not use the styrene-butadiene copolymer or the carboxy-modified styrene-butadiene copolymer as the thermoplastic resin for the under layer, the blocking property was inferior.
In Comparative Example 7, since only benzotriazole was used as the hot-melt material of the heat-sensitive adhesive layer, the adhesive strength at low temperature was extremely inferior.
Since Comparative Example 8 did not contain a silicone resin, the blocking resistance was slightly inferior.
In Comparative Example 9, only triphenylphosphine was used as the heat-melting substance of the heat-sensitive adhesive layer, and a styrene-butadiene copolymer was used as the thermoplastic resin of the under layer, but the adhesive strength was weak and the blocking resistance was slightly higher. It was inferior.

  The heat-sensitive adhesive material of the present invention has a strong adhesive force in a low temperature (0 ° C.) to high temperature (40 ° C.) environment, and there is little decrease in adhesive force over time. In addition, the adhesive strength is strong even immediately after pasting due to the blending of triphenylphosphine and benzotriazole, thermal activation with a thermal head is possible with low energy, and blocking resistance is also good. For example, polyolefin (polyethylene, polypropylene, etc.) Etc.), acrylic, polyethylene terephthalate (PET), polystyrene, nylon and other resin plates; SUS, aluminum and other metal plates; envelopes, cardboard and other paper products; polyolefin wraps; polyvinyl chloride wraps, polyethylene It can be applied to non-woven fabric made of Ellen (envelopes and the like), and in particular, it has a strong adhesive force to rough surface adherends such as cardboard and can be firmly attached.

Claims (8)

On one side of the support, it has at least an under layer and a heat-sensitive adhesive layer in this order, and the under layer contains a thermoplastic resin having a glass transition temperature (Tg) of −35 to 25 ° C. and a hollow filler. And the thermoplastic resin contains a styrene-butadiene copolymer or a carboxy-modified styrene-butadiene copolymer, and the heat-sensitive adhesive layer comprises a thermoplastic resin, a tackifier, a hot melt substance, and silicone resin particles And a heat-sensitive adhesive material, wherein the hot-melt material is triphenylphosphine and a benzotriazole compound represented by the following general formula (1).

(Wherein, R ^1, R ^2, which may be the same or different from each other, represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, alpha, any of α- dimethylbenzyl, R ³ is Represents a hydrogen atom or a chlorine atom.)   The heat-sensitive adhesive material according to claim 1, wherein the content of triphenylphosphine in the hot-melt material is 80 to 90% by weight. The heat-sensitive adhesive material according to claim 1 or 2 , wherein the hollow filler is a spherical hollow particle having a volume average particle diameter of 2.0 to 5.0 µm, and the hollow ratio of the spherical hollow particle is 70% or more.   The material of the spherical hollow particles is any one of vinylidene chloride-acrylonitrile copolymer, acrylonitrile-vinylidene chloride-methyl methacrylate copolymer, and acrylonitrile-methacrylonitrile-isobornyl methacrylate copolymer. Heat sensitive adhesive material.   The heat-sensitive adhesive material according to any one of claims 1 to 4, wherein a mixing ratio of the thermoplastic resin and the hollow filler in the under layer is 0.1 to 2 parts by weight of the hollow filler with respect to 1 part by weight of the thermoplastic resin. The heat-sensitive adhesive material according to any one of claims 1 to 5 , wherein the dry adhesion amount of the heat-sensitive adhesive layer adjacent to the under layer is 10 to ²⁰ g / m2. 7. The support according to any one of claims 1 to 6 , which has at least a heat-sensitive recording layer on a surface of the support which does not have a heat-sensitive adhesive layer, and the heat-sensitive recording layer contains at least a leuco dye and a developer. Heat sensitive adhesive material. The heat-sensitive adhesive material according to any one of claims 1 to 7 , wherein the shape is any one of a label shape, a sheet shape, a label sheet shape, and a roll shape.